Herbicidal composition

ABSTRACT

A selectively herbicidal composition for controlling grasses and weeds in crops of useful plants, comprising
         a) a herbicidally effective amount of a compound of formula I 
                 
 
or a salt or diastereoisomer of a compound of formula I, and
   b) an amount, which is effective for antagonism of the herbicide, of a compound of formula IIa

The present invention relates to new selectively herbicidal compositionsfor controlling grasses and weeds in crops of useful plants, especiallyin crops of cereals, maize and sorghum, which compositions comprise aherbicide and a safener (counter-agent, antidote) and protect the usefulplants, but not the weeds, against the phytotoxic action of theherbicide, and also to the use of the compositions for controlling weedsin crops of useful plants.

When using herbicides, the cultivated plants may also sufferconsiderable damage, depending on, for example, the amount of herbicideand the method of application, the species of cultivated plant, thenature of the soil and climatic conditions, for example hours ofdaylight, temperature and amounts of rainfall. In order to deal withthat and similar problems, various substances have already been proposedas safeners, which are capable of antagonising the harmful effect of theherbicide on the cultivated plant, that is to say are capable ofprotecting the cultivated plant, without appreciably impairing theherbicidal action on the weeds to be controlled. It has been found thatthe proposed safeners often act very specifically both with respect tothe cultivated plants and with respect to the herbicide, and in somecases also in dependence on the method of application, that is to say, aparticular safener is often suitable only for a particular cultivatedplant and a specific class of herbicidal substance or a particularherbicide. For example, WO 96/21652 and WO 99/47525 disclose compoundsthat protect the cultivated plants from the phytotoxic action ofherbicides such as, for example, 3-hydroxy-4-aryl-5-oxopyrazolinederivatives.

It has now been found that compounds of formula IIa

are suitable for protecting cultivated plants from the phytotoxic actionof a particular class of specific, substituted3-hydroxy-4-aryl-5-oxopyrazoline herbicides.

Accordingly, a selectively herbicidal composition is proposed accordingto the invention which, in addition to customary inert formulationassistants, for example carriers, solvents and wetting agents, comprisesas active ingredient a mixture of

-   -   a) a herbicidally effective amount of a herbicide of formula I        wherein    -   R₁ and R₃ are, each independently of the other, ethyl,        haloethyl, ethynyl, C₁- or C₂-alkoxy, C₁- or C₂-haloalkoxy, C₁-        or C₂-alkylcarbonyl or C₁- or C₂-hydroxyalkyl;    -   R₄ and R₅ together are a group Z₂        —CR₁₄(R₁₅)—CR₁₆(R₁₇)—O—CR₁₈(R₁₉)—CR₂₀(R₂₁)— (Z₂);    -   R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ are, each        independently of the others, hydrogen, halogen, C₁-C₄alkyl or        C₁-C₄haloalkyl, wherein an alkylene ring may be fused or        spiro-bound to the carbon atoms of the group Z₂, which alkylene        ring, together with the carbon atoms of the group Z₂, to which        it is bonded, contains from 2 to 6 carbon atoms and may be        interrupted by oxygen, or the alkylene ring bridges at least one        ring atom of the group Z₂;    -   G is hydrogen, —C(X₁)—R₃₀, —C(X₂)—X₃—R₃₁, —C(X₄)—NR₃₂(R₃₃),        —S(O)₂—R₃₄, —P(X₅)R₃₅R₃₆, —CH₂—X₆—R₃₇ or an alkali metal,        alkaline earth metal, sulfonium or ammonium cation;    -   X₁, X₂, X₃, X₄, X₅ and X₆ are, each independently of the others,        oxygen or sulfur;    -   R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇ are, each        independently of the others, hydrogen, C₁-C₁₀alkyl,        C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl,        C₁-C₁₀aminoalkyl, C₂-C₅-alkenyl, C₂-C₅haloalkenyl,        C₃-C₈cycloalkyl, C₁-C₅alkylamino-C₁-C₅alkyl,        di(C₁-C₅alkyl)amino-C₁-C₅alkyl, C₃-C₇cycloalkyl-C₁-C₅alkyl,        C₁-C₅alkoxy-C₁-C₅alkyl, C₃-C₅alkenyloxy-C₁-C₅alkyl,        C₃-C₅alkynyloxy-C₁-C₅alkyl, C₁-C₅alkylthio-C₁-C₅alkyl,        C₁-C₅alkylsulfoxy-C₁-C₅alkyl, C₁-C₅-alkylsulfonyl-C₁-C₅alkyl,        C₂-C₈alkylideneaminooxy-C₁-C₅alkyl,        C₁-C₅alkylcarbonyl-C₁-C₅alkyl, C₁-C₅alkoxycarbonyl-C₁-C₅alkyl,        C₁-C₅alkylaminocarbonyl-C₁-C₅alkyl,        di(C₁-C₅alkyl)aminocarbonyl-C₁-C₅alkyl,        C₁-C₅alkylcarbonylamino-C₁-C₅alkyl,        C₁-C₅alkylcarbonyl-(C₁-C₅alkyl)-amino-C₁-C₅alkyl, tri(C₁- or        C₂-alkyl)silyl-C₁-C₅alkyl, phenyl, heteroaryl,        phenyl-C₁-C₅alkyl, heteroaryl-C₁-C₅alkyl, phenoxy-C₁-C₅alkyl or        heteroaryloxy-C₁-C₅alkyl, wherein the aforementioned aromatic        rings may be substituted by halogen, nitro, cyano, amino,        di(C₁-C₄alkyl)-amino, hydroxy, methoxy, ethoxy, methylthio,        ethylthio, formyl, acetyl, propionyl, carboxyl,        C₁-C₅alkoxycarbonyl or by C₁- or C₂-haloalkyl;    -   R₃₄, R₃₅ and R₃₆ are, in addition, C₁-C₁₀alkoxy,        C₁-C₁₀haloalkoxy, C₁-C₅alkylamino, di(C₁-C₅-alkyl)amino,        benzyloxy or phenoxy, wherein the aromatic rings of the last two        substituents may be substituted by halogen, nitro, cyano, amino,        dimethylamino, hydroxy, methoxy, ethoxy, methylthio, ethylthio,        formyl, acetyl, propionyl, carboxyl, C₁-C₅alkoxycarbonyl or by        C₁- or C₂-haloalkyl; and    -   R₃₇ is, in addition, C₁-C₁₀alkylcarbonyl,    -   or a salt or diastereoisomer of a compound of formula I, and    -   b) an amount, which is effective for antagonism of the        herbicide, of a safener of formula IIa        wherein    -   R₂₂ is hydrogen, or an alkali metal, alkaline earth metal,        sulfonium or ammonium cation, or ethyl,    -   or of formula IIb        wherein    -   R₂₃ is hydrogen, or an alkali metal, alkaline earth metal,        sulfonium or ammonium cation, or ethyl,    -   or of formula IIc        wherein    -   R₂₄ and R₂₅ are, each independently of the other, hydrogen,        C₁-C₆alkyl, C₂-C₆-alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkyl;    -   R₂₆ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₆haloalkyl or        C₁-C₆haloalkoxy; or the radicals R₂₆ are, each independently of        the other(s), hydrogen, halogen, C₁-C₄alkyl, C₁-C₆haloalkyl or        C₁-C₆haloalkoxy;    -   R₂₇ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl,        C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄-alkylthio,        C₁-C₄alkoxycarbonyl or nitro; or the radicals R₂₇ are, each        independently of the other, hydrogen, halogen, C₁-C₄alkyl,        C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄-alkylthio,        C₁-C₄alkoxycarbonyl or nitro;    -   n is 0, 1, 2 or 3; and    -   m is 1 or 2,    -   or of formula IId        wherein    -   R₂₈ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkylthio,        C₃-C₈cycloalkyl, phenyl, phenyl-C₁-C₆alkyl or heteroaryl,        wherein the afore-mentioned hydrocarbon radicals may be        substituted by halogen, cyano, nitro, amino, hydroxy, carboxyl,        formyl, carbonamide or by sulfonamide;    -   R₂₉ is hydrogen, C₁-C₆alkyl or C₁-C₄haloalkyl;    -   R₃₀ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl,        C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfonyl, cyano, nitro,        formyl or carboxyl; or the radicals R₃₀ are, each independently        of the other hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl,        C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfonyl, cyano, nitro,        formyl or carboxyl;    -   R₃₁ is hydrogen, C₁-C₆alkyl or C₁-C₄haloalkyl;    -   R₃₂ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl,        C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfonyl, cyano, nitro,        formyl or carboxyl; or the radicals R₃₂ are, each independently        of the other hydogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl,        C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfonyl, cyano, nitro,        formyl or carboxyl; and    -   o and p are, each independently of the other 0, 1 or 2,    -   or of formula IIe        wherein    -   G₂ is hydrogen, formyl, C₁-C₆alkylcarbonyl,        C₂-C₆alkenylcarbonyl, C₂-C₆alkynylcarbonyl, C₁-C₆alkoxycarbonyl,        (C₁-C₆alkylthio)carbonyl, C₃-C₈cycloalkylcarbonyl,        phenyl-C₁-C₆alkylcarbonyl, phenycarbonyl, C₁-C₆alkylsulfonyl,        C₂-C₆alkenylsulfonyl or phenylsulfonyl, wherein the        afore-mentioned hydrocarbon radicals may be substituted by        halogen, cyano, nitro, amino, methoxy, ethoxy or by phenyl;    -   R₃₃ is hydrogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,        C₃-C₈cycloalkyl, formyl, C₁-C₆alkylcarbonyl,        C₂-C₆alkenylcarbonyl, C₂-C₆alkynylcarbonyl, C₁-C₆alkoxycarbonyl,        (C₁-C₆alkylthio)carbonyl, C₃-C₈cycloalkylcarbonyl,        C₁-C₆alkylsulfonyl, C₂-C₆alkenylsulfonyl or phenylsulfonyl,        wherein the afore-mentioned hydrocarbon radicals may be        substituted by halogen, cyano, nitro, amino, methoxy, ethoxy or        by phenyl;    -   R₃₄ is hydrogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,        C₃-C₈cycloalkyl, formyl, C₁-C₆alkylcarbonyl,        C₂-C₆alkenylcarbonyl, C₂-C₆alkynylcarbonyl, C₁-C₆alkoxycarbonyl,        (C₁-C₆alkylthio)carbonyl, C₃-C₈cycloalkylcarbonyl,        C₁-C₆alkylsulfonyl, C₂-C₆alkenylsulfonyl or phenylsulfonyl,        wherein the afore-mentioned hydrocarbon radicals may be        substituted by halogen, cyano, nitro, amino, methoxy, ethoxy or        by phenyl;    -   R₃₅, R₃₆, R₃₇ and R₃₈ are, each independently of the others,        hydrogen, halogen, amino, C₁-C₃alkylamino, di(C₁-C₃alkyl)amino,        hydroxy, cyano, nitro, formyl, carboxyl, C₁-C₆alkoxy,        C₁-C₆haloalkoxy, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl,        C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆-alkenyl or C₂-C₆alkynyl; or    -   R₃₈ and R₃₃, together with the ring atoms to which they are        bonded, form a five- or six-membered saturated or unsaturated        ring that contains up to 2 identical or different hetero atoms        selected from the group oxygen, sulfur and nitrogen and that may        be interrupted by a —C(O)— radical.

Depending on the substituents R₁, R₃, R₄, R₅ and G, the compounds offormula I may be in the form of geometric and/or optical isomers andisomeric mixtures (atropisomers) and, when G is hydrogen, a metal ionequivalent, a sulfonium cation or an ammonium cation, in the form oftautomers and tautomeric mixtures.

The present invention also includes the salts that the compounds offormula I may form with acids. Suitable acids for the formation of acidaddition salts are both organic and inorganic acids. Examples of suchacids are hydrochloric acid, hydrobromic acid, nitric acid, phosphoricacids, sulfuric acid, acetic acid, propionic acid, butyric acid, valericacid, oxalic acid, malonic acid, fumaric acid, organic sulfonic acids,lactic acid, tartaric acid, citric acid and salicylic acid.

The compounds of formula I wherein G is hydrogen can, because of theiracidity, readily be converted, in the presence of bases (protonacceptors), into the corresponding salts (wherein G is, for example, ametal ion equivalent or an ammonium cation), as described, by example,in EP-A-0 508 126. Any conventional proton acceptor can be used as thebase. The salts are, for example, alkali metal salts, e.g. sodium andpotassium salts; alkaline earth metal salts, e.g. calcium and magnesiumsalts; ammonium salts, that is to say unsubstituted ammonium salts andmono- or poly-substituted ammonium salts, e.g. triethylammonium andmethylammonium salts, or are salts with other organic bases or othercations, e.g. sulfonium cations. Sulfonium cations are, for example,tri(C₁-C₄alkyl)sulfonium cations, which can be obtained from thecorresponding alkali metal salts, for example by salt conversion, forexample using a cation exchanger.

Among the alkali metal and alkaline earth metal hydroxides used as saltformers, emphasis is to be given to, for example, the hydroxides oflithium, sodium, potassium, magnesium or calcium, but especially thoseof sodium and potassium. Suitable salt formers are described, forexample, in WO 97/41112.

Examples of suitable amines for ammonium salt formation that come intoconsideration are ammonia as well as primary, secondary and tertiaryC₁-C₁₈alkylamines, C₁-C₄hydroxyalkylamines and C₂-C₄alkoxyalkylamines,for example methylamine, ethylamine, n-propylamine, isopropylamine, thefour butylamine isomers, n-amylamine, isoamylamine, hexylamine,heptylamine, octylamine, nonylamine, decylamine, pentadecylamine,hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine,methyl-isopropylamine, methyl-hexylamine, methyl-nonylamine,methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine,ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine,hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine,diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine,dihexylamine, diheptylamine, dioctylamine, ethanolamine,n-propanolamine, isopropanolamine, isopropanolamine, N,N-diethanolamine,N-ethylpropanolamine, N-butyl-ethanolamine, allylamine,n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine,dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine,triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine,triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamineand ethoxyethylamine; heterocyclic amines, for example pyridine,quinoline, isoquinoline, morpholine, N-methylmorpholine, thiomorpholine,piperidine, pyrrolidine, indoline, quinuclidine and azepine; primaryaryl amines, for example anilines, methoxyanilines, ethoxyanilines, o-,m- and p-toluidines, phenylene-diamines, benzidines, naphthylamines ando-, m- and p-chloroanilines; but especially triethylamine,isopropylamine and diisopropylamine.

In the above definitions, halogen is to be understood as fluorine,chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

The alkyl groups occurring in the substituent definitions are, forexample, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,isobutyl or tert-butyl, and the pentyl, hexyl, heptyl, octyl, nonyl anddecyl isomers.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbonatoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl,difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl,dichlorofluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl,2-fluoroethyl, 2-chloroethyl, 2,2-difluoroethyl, 2,2-dichloroethyl,2,2,2-trichloroethyl or pentafluoroethyl, preferably trichloromethyl,difluoromethyl, difluorochloromethyl, trifluoromethyl ordichlorofluoromethyl.

Alkoxy groups preferably have a chain length of from 1 to 6 carbonatoms. Alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, or a pentyloxy or hexyloxyisomer, preferably methoxy, ethoxy or n-propoxy.

Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy,trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy,2-fluoroethoxy, 2-chloroethoxy or 2,2,2-trichloroethoxy.

There may be mentioned as examples of alkenyl radicals vinyl, allyl,methallyl, 1-methylvinyl, but-2-en-1-yl, pentenyl and 2-hexenyl;preferably alkenyl radicals having a chain length of from 2 to 6 carbonatoms.

There may be mentioned as examples of alkynyl radicals ethynyl,propargyl, 1-methyl-propargyl, 3-butynyl, but-2-yn-1-yl,2-methylbut-3-yn-2-yl, but-3-yn-2-yl, 1-pentynyl, pent-4-yn-1-yl and2-hexynyl; preferably alkynyl radicals having a chain length of from 2to 6 carbon atoms.

Suitable haloalkenyl radicals include alkenyl groups substituted one ormore times by halogen, halogen being in particular bromine or iodine andespecially fluorine or chlorine, for example 2- and 3-fluoropropenyl, 2-and 3-chloropropenyl, 2- and 3-bromopropenyl,2,2-difluoro-1-methylvinyl, 2,3,3-trifluoropropenyl,3,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl,4,4,4-trifluorobut-2-en-1-yl and 4,4,4-trichlorobut-2-en-1-yl. Preferredalkenyl radicals substituted once, twice or three times by halogen arethose having a chain length of from 2 to 5 carbon atoms. The alkenylgroups may be substituted by halogen at saturated or unsaturated carbonatoms.

Alkenyloxy is, for example, allyloxy, methallyloxy or but-2-en-1-yloxy.

Alkynyloxy is, for example, propargyloxy or 1-methylpropargyloxy.

Alkoxyalkyl groups have preferably from 2 to 10 carbon atoms.Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl,ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl orisopropoxyethyl.

Suitable cycloalkyl substituents contain from 3 to 8 carbon atoms andare, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl or cyclooctyl.

Alkylcarbonyl is especially acetyl or propionyl.

Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl,n-propoxycarbonyl, isopropoxycarbonyl or a butoxycarbonyl,pentyloxycarbonyl or hexyloxycarbonyl isomer, preferably methoxycarbonylor ethoxycarbonyl.

Phenyl per se or as part of a substituent, for example phenoxyalkyl orbenzyloxy, may be in substituted form, in which case the substituentsmay, as desired, be in the ortho-, meta- and/or para-position. Preferredpositions for the substituents are the ortho- and para-position to thering attachment point. Phenyl substituents are, for example, halogen,C₁- or C₂-haloalkyl, hydroxy, C₁- or C₂-alkoxy, C₁-C₅alkoxycarbonyl, C₁-or C₂alkylthio, formyl, acetyl, propionyl, carboxyl, nitro, cyano, aminoor dimethylamino.

Alkylthio groups preferably have a chain length of from 1 to 5 carbonatoms. Alkylthio is, for example, methylthio, ethylthio, propylthio,butylthio, pentylthio or hexylthio, or a branched isomer thereof, but ispreferably methylthio or ethylthio.

Alkylsulfoxy is, for example, methylsulfoxy, ethylsulfoxy,n-propylsulfoxy, isopropylsulfoxy, n-butylsulfoxy, isobutylsulfoxy,sec-butylsulfoxy or tert-butylsulfoxy, preferably methylsulfoxy orethylsulfoxy.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl,n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl,sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl orethylsulfonyl.

Alkylamino is, for example, methylamino, ethylamino, n-propylamino,isopropylamine or a butyl- or pentyl-amine isomer.

Dialkylamino is, for example, dimethylamino, methylethylamino,diethylamino, n-propyl-methylamino, dibutylamino or diisopropylamino.

Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl,ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl,isopropylthiomethyl or isopropylthioethyl.

Hydroxyalkyl is, for example, hydroxymethyl, 2-hydroxyethyl or3-hydroxypropyl.

Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-1-yl orcyanopropyl.

Aminoalkyl is, for example, aminomethyl, aminoethyl, aminoeth-1-yl oraminopropyl.

Nitroalkyl is, for example, nitromethyl, 2-nitroethyl or 3-nitropropyl.

Alkylideneaminooxy-alkyl radicals are oxime ether substituents, forexample having the following structure

Carbonamide and sulfonamide radicals, for example in the definition ofR₂₈, have the structures —C(O)NH₂ and —S(O)₂NH₂, respectively.

Heteroaryl radicals per se or as part of a substituent, for exampleheteroaryloxy-alkyl, are usually 5- or 6-membered aromatic heterocyclesthat contain preferably from 1 to 3 hetero atoms, such as N, S and/or O.Examples of suitable heteroaryl radicals are pyridyl, pyrimidyl,thienyl, triazinyl, thiazolyl, triazolyl, thiadiazolyl, imidazolyl,oxazolyl, isoxazolyl, pyrazinyl, furyl, pyrazolyl, benzoxazolyl,benzothiazolyl, quinoxalyl, indolyl and quinolyl. Those hetero-aromaticradicals may, in addition, be substituted, for example by halogen, C₁-or C₂-halo-alkyl, hydroxy, C₁- or C₂-alkoxy, C₁- or C₂alkylthio, formyl,acetyl, propionyl, carboxyl, C₁-C₅-alkoxycarbonyl, amino, dimethylamino,nitro or by cyano.

Meanings corresponding to those given hereinbefore can also be ascribedto the substituents in composite definitions, such as, for examplealkylamino-alkyl, dialkylamino-alkyl, cycloalkyl-alkyl,alkenyloxy-alkyl, alkynyloxy-alkyl, alkylsulfoxy-alkyl,alkylsulfonyl-alkyl, alkylcarbonyl-alkyl, alkoxycarbonyl-alkyl,alkylaminocarbonyl-alkyl, dialkylaminocarbonyl-alkyl,alkylcarbonylamino-alkyl, alkylcarbonyl(alkyl)-amino-alkyl, phenyl-alkyland heteroaryl-alkyl.

Compounds of formula I wherein an alkylene ring may be fused orspiro-bound to the group Z₂, which alkylene ring, together with thecarbon atoms of the group Z₂, contains from 2 to 6 carbon atoms, have,for example, the following structure

Compounds of formula I wherein in the group Z₂ an alkylene ring bridgesat least one ring atom of the group Z₂ have, for example, the followingstructure

In the definitions for cyanoalkyl, alkylcarbonyl, alkylcarbonylamino andalkoxycarbonyl, the carbon atom of the cyano or carbonyl is not includedin the lower and upper limits given for the number of carbons in eachparticular case.

The compounds of formula I, except for those derivatives wherein G is—CH₂—X₆—R₂₇, are known from WO 99/47525 and can be prepared analogouslyto the methods described therein and in EP-A-0 508 126.

The compounds of formula IIa are known from DE-A-3 939 503, those offormula IIb from DE-A-4 331 448, those of formula IIc from WO 99/16744,those of formula IId from WO 00/30447 and those of formula IIe from WO00/00020.

The compounds of formula Ia

wherein R₁, R₃, R₄, R₅, R₃₇ and X₆ are as defined for formula I, are newand are therefore also included in the present invention.

The compounds of formula Ia can be prepared using processes known perse, for example by converting a compound of formula Ib

in an inert solvent, for example an aromatic hydrocarbon, e.g. benzene,toluene or a xylene; a chlorinated hydrocarbon, e.g. dichloromethane orchlorobenzene; a ketone, e.g. acetone or 2-butanone; a nitrile, e.g.acetonitrile or propionitrile; an ether, e.g. diethyl ether,tert-butyl-methyl ether or di-n-propyl ether; an ester, e.g. ethylacetate; an amide, e.g. N,N-dimethyl-formamide or N-methylpyrrolidone(NMP); a sulfoxide, e.g. dimethyl sulfoxide (DMSO) or a sulfone, e.g.sulfolane, in the presence of a base, for example an alkylamine, e.g.triethylamine or diisopropylethylamine; an alicyclic or aromatic amine,e.g. 1,4-diazabicyclo[2.2.2]-octane (DABCO) or1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or pyridine; a carbonate, e.g.sodium or potassium carbonate, or sodium or potassium bicarbonate, intothe corresponding salt of formula Ic

wherein the radicals R₁, R₃, R₄ and R₅ in the compounds of formulae Iband Ic are as defined for formula I and G₀ is an alkali metal, alkalineearth metal, ammonium or sulfonium cation, depending on the base used,and then reacting the compound of formula Ic with a compound of formulaIIIR₃₇—X₆—CH₂—Y   (III),wherein R₃₇ and X₆ are as defined for formula I and Y is a leavinggroup, for example halogen, e.g. chlorine, bromine or iodine, attemperatures of from −20° C. to reflux temperature, preferably at from0° C. to the reflux temperature of the solvent used.

The Example that follows illustrates the preparation of compounds offormula Ia.

EXAMPLE P1 Preparation of

0.753 g of pivalic acid chloromethyl ester is added to 0.75 g of sodiumiodide dissolved in 20 ml of acetone, and the reaction mixture isstirred overnight at 25° C. The reaction mixture is cooled to 5° C.;1.58 g of8-(2,6-diethyl-4-methylphenyl)tetrahydropyrazolo[1,2-d][1,4,5]-oxadiazepine-7,9-dioneand 0.69 g of potassium carbonate are added and the reaction mixture isstirred first for one hour at 5° C. and then for 24 hours at 25° C. Theresulting reaction mixture is filtered and the filtrate is concentratedby evaporation under reduced pressure. The residue is dissolved in 100ml of ethyla acetate, washed with water until neutral, dried over sodiumsulfate and concentrated by evaporation.

The preferred compounds of formula Ia listed in Table 1 below areprepared in an analogous manner.

TABLE 1 Compounds of formula Ia (Ia)

Comp. No. R₁ R₃ —X₆—R₃₇ Phys. data 1.001 —C₂H₅ —C₂H₅ —O—C(O)C(CH₃)₃¹H-NMR (300 MHz, CDCl₃): 6.90 ppm (s, 2H); 5.20 ppm (s, 2H); 4.10 ppm(m,2H); 3.85 ppm (m, 2H); 3.80 ppm(s, 4H); 2.80 ppm (s, 3H); 2.50 ppm(m,4H); 1.15 ppm (t, 6H); 1.15 ppm (s, 9H). 1.002 —C₂H₅ —C₂H₅ —S—CH₃ 1.003—C₂H₅ —C₂H₅ —O—CH₃ 1.004 —C₂H₅ —C≡CH —O—CH₃ 1.005 —C₂H₅ —OCH₃ —O—CH₃1.006 —C₂H₅ —C₂H₅ —O—C₂H₅ 1.007 —C₂H₅ —C₂H₅ —O—(CH₂)₂—O—CH₃ 1.008 —C₂H₅—C≡CH —O—C₂H₅ 1.009 —C₂H₅ —C₂H₅ —S—CH₃ 1.010 —C₂H₅ —C₂H₅ —O—C(O)—C(CH₃)₃

Herbicides of formula I that are preferred for the composition accordingto the invention are those wherein R₁ and R₃ are, each independently ofthe other, ethyl, haloethyl, ethynyl, C₁- or C₂-alkoxy or C₁- orC₂-haloalkoxy.

In a further group of preferred compounds of formula I, R₄ and R₅together form a group of Z₂ —CR₁₄(R₁₅)—CR₁₆(R₁₇)—O—CR₁₈(R₁₉)—CR₂₀(R₂₁)—(Z₂), wherein R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ are hydrogen.

Preference is given also to those compounds of formula I wherein G ishydrogen, —C(X₁)—R₃₀, —C(X₂)—X₃—R₃₁, —C(X₄)—NR₃₂(R₃₃), —S(O)₂—R₃₄,—P(X₅)R₃₅R₃₆, —CH₂—X₆—R₃₇ or an alkali metal, alkaline earth metal,sulfonium or ammonium cation; X₁, X₂, X₃, X₄, X₅ and X₆ are, eachindependently of the others, oxygen or sulfur; R₃₀, R₃₁, R₃₂, R₃₃, R₃₄,R₃₅, R₃₆ and R₃₇ are, each independently of the others, hydrogen,C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈cyanoalkyl, C₁-C₈nitroalkyl,C₁-C₈aminoalkyl, C₂-C₅-alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl,C₁-C₅alkylamino-C₁-C₂alkyl, di(C₁-C₅alkyl)amino-C₁-C₂alkyl,C₃-C₇cycloalkyl-C₁-C₂alkyl, C₁-C₄alkoxy-C₁-C₄alkyl,C₂-C₄alkenyloxy-C₁-C₄alkyl, C₃-C₄alkynyloxy-C₁-C₄alkyl,C₁-C₄alkylthio-C₁-C₄alkyl, C₁-C₂alkylsulfoxy-C₁-C₂alkyl,C₁-C₂-alkylsulfonyl-C₁-C₂alkyl, C₂-C₈alkylideneaminooxy-C₁-C₂alkyl,C₁-C₅alkylcarbonyl-C₁-C₂alkyl, C₁-C₅alkoxycarbonyl-C₁-C₂alkyl,C₁-C₅alkylaminocarbonyl-C₁-C₂alkyl,di(C₁-C₄alkyl)aminocarbonyl-C₁-C₂alkyl,C₁-C₅alkylcarbonylamino-C₁-C₂alkyl,C₁-C₂alkylcarbonyl-(C₁-C₃alkyl)-amino-C₁-C₂alkyl, tri(C₁- orC₂-alkyl)silyl-C₁-C₃-alkyl, phenyl, heteroaryl, phenyl-C₁-C₂alkyl,heteroaryl-C₁-C₂alkyl, phenoxy-C₁-C₂alkyl or heteroaryloxy-C₁-C₂alkyl;R₃₄, R₃₅ and R₃₆ are, in addition, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₁-C₃alkylamino, di(C₁-C₃alkyl)amino, benzyloxy or phenoxy, wherein thearomatic rings of the last two substituents may be substituted byhalogen, nitro, cyano, amino, dimethylamino, hydroxy, methoxy, ethoxy,methylthio, ethylthio, formyl, acetyl, propionyl, carboxyl,C₁-C₅-alkoxycarbonyl or by C₁- or C₂-haloalkyl; and R₃₇ is, in addition,C₁-C₈alkylcarbonyl.

Among those, special preference is given to those compounds wherein G ishydrogen, —C(X₁)—R₃₀, —C(X₂)—X₃—R₃₁, —C(X₄)—NR₃₂(R₃₃), —S(O)₂—R₃₄,—P(X₅)R₃₅R₃₆, —CH₂—X₆—R₃₇ or an alkali metal, alkaline earth metal,sulfonium or ammonium cation; X₁, X₂, X₃, X₄, X₅ and X₆ are, eachindependently of the others, oxygen or sulfur; R₃₀, R₃₁, R₃₂, R₃₃, R₃₄,R₃₅, R₃₆ and R₃₇ are, each independently of the others, hydrogen,C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈alkenyl, C₂-C₅haloalkenyl,C₃-C₈cycloalkyl, C₃-C₇cycloalkyl-C₁-C₂alkyl, C₁-C₄alkoxy-C₁-C₄alkyl,phenyl, heteroaryl, phenyl-C₁-C₂alkyl, heteroaryl-C₁-C₂alkyl,phenoxy-C₁-C₂alkyl or heteroaryloxy-C₁-C₂alkyl; R₃₄, R₃₅ and R₃₆ are, inaddition, C₁-C₆alkoxy, C₁-C₃alkylamino or di(C₁-C₃alkyl)amino; and R₃₇is, in addition, C₁-C₈alkylcarbonyl.

Preference is also given to those compounds of formula I wherein G is—CH₂—X₆—R₃₇ and X₆ and R₃₇ are as defined for formula I.

Preference is likewise given to compounds of formula I wherein R₁ or R₃is, or R₁ and R₃ are, each independently of the other C₁- orC₂-haloalkoxy or C₁- or C₂-hydroxyalkyl.

Preference is also given to compounds of formula I wherein G is—C(X₁)—R₃₀, —C(X₂)—X₃—R₃₁, —C(X₄)—NR₃₂(R₃₃), —S(O)₂—R₃₄ or —P(X₅)R₃₅R₃₆;X₁, X₂, X₃, X₄ and X₅ are, each independently of the others, oxygen orsulfur; R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅ and R₃₆ are, each independently ofthe others, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl,C₁-C₅alkylamino-C₁-C₅alkyl, di(C₁-C₅alkyl)amino-C₁-C₅-alkyl,C₃-C₇cycloalkyl-C₁-C₅alkyl, C₃-C₅alkenyloxy-C₁-C₅alkyl,C₃-C₅alkynyloxy-C₁-C₅alkyl, C₁-C₅alkylthio-C₁-C₅alkyl,C₁-C₅alkylsulfoxy-C₁-C₅alkyl, C₁-C₅alkylsulfonyl-C₁-C₅alkyl,C₂-C₈-alkylideneaminooxy-C₁-C₅alkyl, C₁-C₅alkylcarbonyl-C₁-C₅alkyl,C₁-C₅alkoxycarbonyl-C₁-C₅-alkyl, C₁-C₅alkylaminocarbonyl-C₁-C₅alkyl,di(C₁-C₅alkyl)aminocarbonyl-C₁-C₅alkyl,C₁-C₅-alkylcarbonylamino-C₁-C₅alkyl,C₁-C₅alkylcarbonyl-(C₁-C₅alkyl)-amino-C₁-C₅alkyl, tri(C₁- orC₂-alkyl)silyl-C₁-C₅alkyl, phenyl-C₁-C₅alkyl, heteroaryl-C₁-C₅alkyl,phenoxy-C₁-C₅alkyl or heteroaryloxy-C₁-C₅alkyl, wherein theafore-mentioned aromatic rings may be substituted by halogen, nitro,cyano, amino, di(C₁-C₄alkyl)amino, hydroxy, methoxy, ethoxy, methylthio,ethylthio, formyl, acetyl, propionyl, carboxyl, C₁-C₅alkoxycarbonyl orby C₁- or C₂-haloalkyl; and R₃₄, R₃₅ and R₃₆ are, in addition,C₁-C₁₀alkoxy, C₁-C₁₀haloalkoxy, C₁-C₅alkylamino, di(C₁-C₅-alkyl)amino,benzyloxy or phenoxy, wherein the aromatic rings of the last twosubstituents may be substituted by halogen, nitro, cyano, amino,dimethylamino, hydroxy, methoxy, ethoxy, methylthio, ethylthio, formyl,acetyl, propionyl, carboxyl, C₁-C₅alkoxycarbonyl or by C₁- orC₂-haloalkyl.

Preferred selectively herbicidal compositions are those which compriseas active ingredient a mixture of a) a herbicidally effective amount ofa herbicide of formula I, wherein

-   -   R₁, R₃, R₄, R₅ and G are as defined for formula I,        and b) an amount, which is effective for antagonism of the        herbicide, of a safener of formula IIa, wherein    -   R₂₂ is as defined for formula IIa,        or of formula IIb, wherein    -   R₂₃ is as defined for formula IIb,        or of formula IIc, wherein    -   R₂₄ and R₂₅ are, each independently of the other, hydrogen,        C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆-alkynyl or C₃-C₆cycloalkyl;    -   R₂₆ is halogen, C₁-C₄alkyl or C₁-C₄haloalkyl;    -   R₂₇ is halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy,        C₁-C₄alkylthio, C₁-C₄alkoxycarbonyl or nitro;    -   n is 0, 1, 2 or 3; and    -   m is 1 or 2.

Safeners of formula IIa preferred for the composition according to theinvention are those wherein R₂₂ is hydrogen or an alkali metal, alkalineearth metal, sulfonium or ammonium cation.

Safeners of formulae IIa and IIb preferred for the composition accordingto the invention are those wherein R₂₂ and R₂₃ are ethyl and arereferred to hereinafter as safeners of formulae IIa, and IIb,(Biological Examples). They are known under the names mefenpyr-ethyl(compound no. IIa₁) and isoxadifen-ethyl (compound no. IIb₁) (ISOproposed names).

Safeners of formula IId preferred for the composition according to theinvention are those wherein R₂₈ is hydrogen, C₁-C₆alkyl, C₃-C₈cycloalkylor phenyl, wherein the afore-mentioned hydrocarbon radicals may besubstituted by halogen, cyano, nitro, amino, hydroxy, carboxyl, formyl,carbonamide or by sulfonamide; R₂₉ is hydrogen; R₃₀ is hydrogen,halogen, C₁-C₄-alkyl, alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy,C₁-C₄alkylthio, cyano, nitro or formyl; or the radicals R₃₀ are, eachindependently of the other, hydrogen, halogen, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄-alkoxy, C₁-C₄alkylthio, cyano, nitro or formyl;R₃₁ is hydrogen; R₃₂ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄alkoxy, C₁-C₄alkylthio, cyano, nitro or formyl; or the radicals R₃₂are, each independently of the other, hydrogen, halogen, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, cyano, nitro or formyl; ando and p are, each independently of the other, 0, 1 or 2.

Safeners of formula IId that are especially preferred for thecomposition according to the invention are:

-   -   2-methoxy-N-[4-(2-methoxybenzoylsulfamoyl)phenyl]acetamide;    -   N-[4-(2-methoxybenzoylsulfamoyl)phenyl]cyclopropanecarboxamide;    -   N-[4-(2-methoxybenzoylsulfamoyl)phenyl]cyclobutanecarboxamide;    -   N-[4-(2-chlorobenzoylsulfamoyl)phenyl]cyclopropanecarboxamide;    -   N-[4-(2-chlorobenzoylsulfamoyl)phenyl]acetamide;    -   N-[4-(2-trifluoromethoxybenzoylsulfamoyl)phenyl]acetamide;    -   N-[4-(2-trifluoromethylbenzoylsulfamoyl)phenyl]cyclopropanecarboxamide;    -   N-[4-(2-trifluoromethoxybenzoylsulfamoyl)phenyl]cyclopropanecarboxamide;    -   N-[4-(2-trifluoromethoxybenzoylsulfamoyl)phenyl]cyclobutanecarboxamide;        and    -   N-[4-(2-trifluoromethylbenzoylsulfamoyl)phenyl]acetamide.

Safeners of formula IIe preferred for the composition according to theinvention are those wherein G₂ is hydrogen, formyl, C₁-C₆alkylcarbonyl,C₂-C₆alkenylcarbonyl, C₂-C₆alkynylcarbonyl, C₁-C₆alkoxycarbonyl,(C₁-C₆alkylthio)carbonyl, C₃-C₈cycloalkylcarbonyl,phenyl-C₁-C₆alkylcarbonyl or phenylcarbonyl, wherein the afore-mentionedhydrocarbon radicals may be substituted by halogen, cyano, nitro, amino,methoxy, ethoxy or by phenyl; R₃₃ is hydrogen, C₁-C₆alkyl, C₂-C₆alkenyl,C₂-C₆alkynyl, formyl, C₁-C₆alkylcarbonyl or C₁-C₆alkoxycarbonyl, whereinthe afore-mentioned hydrocarbon radicals may be substituted by halogen,cyano, nitro, amino, methoxy, ethoxy or by phenyl; R₃₄ is hydrogen,C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, formyl, C₁-C₆alkylcarbonyl orC₁-C₆-alkoxycarbonyl, wherein the afore-mentioned hydrocarbon radicalsmay be substituted by halogen, cyano, nitro, amino, methoxy, ethoxy orby phenyl; R₃₅, R₃₆, R₃₇ and R₃₈ are, each independently of the others,hydrogen, halogen, cyano, nitro, formyl, carboxyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkyl orC₁-C₆haloalkyl; or R₃₈ and R₃₃, together with the ring atoms to whichthey are bonded, form a five- or six-membered saturated or unsaturatedring that contains up to 2 identical or different hetero atoms selectedfrom the group oxygen, sulfur and nitrogen and that may be interruptedby a —C(O)— radical.

Among those, special preference is given to those compounds wherein G₂is hydrogen, formyl, C₁-C₆alkylcarbonyl, C₂-C₆alkenylcarbonyl,C₂-C₆alkynylcarbonyl, C₁-C₆alkoxycarbonyl, (C₁-C₆alkylthio)carbonyl,C₃-C₈cycloalkylcarbonyl or phenylcarbonyl; R₃₃ is hydrogen, C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆alkynyl, formyl, C₁-C₆alkylcarbonyl orC₁-C₆alkoxycarbonyl; R₃₄ is hydrogen, C₁-C₆alkyl, C₂-C₆alkenyl,C₂-C₆alkynyl, formyl, C₁-C₆alkylcarbonyl or C₁-C₆-alkoxycarbonyl; R₃₅,R₃₆, R₃₇ and R₃₈ are, each independently of the others, hydrogen,halogen, cyano, nitro, formyl, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxyor C₁-C₆haloalkoxy; or R₃₈ and R₃₃, together with the ring atoms towhich they are bonded, form a five- or six-membered saturated orunsaturated ring that contains up to 2 identical or different heteroatoms selected from the group oxygen, sulfur and nitrogen and that maybe interrupted by a —C(O)— radical.

Safeners of formula IIe that are especially preferred for thecomposition according to the invention are:

-   -   4-hydroxy-1-methyl-3-(1H-tetrazole-5-carbonyl)-1H-quinolin-2-one;    -   1-ethyl-4-hydroxy-3-(1H-tetrazole-5-carbonyl)-1H-quinolin-2-one;    -   6-hydroxy-5-(1H-tetrazole-5-carbonyl)-1,2-dihydro-pyrrolo[3,2,1-H]quinolin-4-one;    -   3-(1-acetyl-1H-tetrazole-5-carbonyl)-4-hydroxy-1-methyl-1H-quinolin-2-one;    -   6-chloro-4-hydroxy-1-methyl-3-(1H-tetrazole-5-carbonyl)-1H-quinolin-2-one;    -   6-fluoro-4-hydroxy-1-methyl-3-(1H-tetrazole-5-carbonyl)-1H-quinolin-2-one;    -   4-hydroxy-1,6-dimethyl-3-(1H-tetrazole-5-carbonyl)-1H-quinolin-2-one;    -   4-hydroxy-6-methoxy-1-methyl-3-(1H-tetrazole-5-carbonyl)-1H-quinolin-2-one;    -   1-methyl-2-oxo-3-(1H-tetrazole-5-carbonyl)-1,2-dihydroquinolin-4-yl        acetate; and    -   1-methyl-2-oxo-3-(1H-tetrazole-5-carbonyl)-1,2-dihydroquinolin-4-yl        2,2-dimethyl propionate.

The invention relates also to a method for the selective control ofweeds in crops of useful plants, which method comprises treating theuseful plants, their seeds or seedlings or the crop area thereof with,simultaneously or separately,

-   -   a) a herbicidally effective amount of a herbicide of formula I,    -   b) an amount, which is effective for antagonism of the        herbicide, of a safener of formula II and, optionally,    -   c) an additive comprising an oil of vegetable origin or an        alkylated derivative thereof, or a mineral oil or a mixture        thereof.

Cultivated plants that may be protected against the harmful effect ofthe above-mentioned herbicides by means of the safeners of formula IIare especially cereals, maize and sorghum. Crops are to be understood asincluding those that have been made tolerant to herbicides or classes ofherbicides by means of conventional breeding or genetic engineeringmethods, for example IMI Maize, Poast Protected Maize (Sethoxydimtolerance), Liberty Link Maize, B.t./Liberty Link Maize, IMI/LibertyLink Maize, IMI/Liberty Link/B.t. Maize, Roundup Ready Maize and RoundupReady/B.t. Maize. The weeds to be controlled may be both monocots anddicots, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena,Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria,Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus,Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea,Chrysanthemum, Galium, Viola and Veronica.

Crop areas are areas of land on which the cultivated plants are alreadygrowing or in which the seeds of those cultivated plants have been sown,and also areas of land on which it is intended to grow those cultivatedplants.

A safener of formula II may, depending on the intended purpose, be usedto pre-treat the seed material of the cultivated plant (dressing theseed or the seedlings) or may be incorporated into the soil before orafter sowing. It may, however, also be applied, alone or together withthe herbicide and, optionally, the oil additive, after the emergence ofthe plants. The treatment of the plants or seed with the safener cantherefore, in principle, be effected independently of the time at whichthe herbicide is applied. The treatment of the plant can, however, alsobe carried out by applying the herbicide and the safener simultaneously(for example in the form of a tank mixture). The rate of application ofthe safener in relation to the herbicide depends largely on the methodof application. In the case of field treatment, which is effected eitherusing a tank mixture with a combination of the safener and the herbicideor by the separate application of the safener and the herbicide, theratio of herbicide to safener is generally from 1:100 to 100:1,preferably from 1:10 to 10:1, and especially from 1:5 to 5:1.

In the case of field treatment, from 0.001 to 5.0 kg safener/ha,preferably from 0.001 to 0.5 kg safener/ha, are generally applied. Therate of application of herbicide is generally from 0.001 to 2 kg/ha, butpreferably from 0.005 to 0.5 kg/ha.

In addition to the conventional formulation adjuvants, oil additives c)may be introduced as additives into the spray tank (as a tank mixture),besides surfactants and salts. In the composition according to theinvention, the amounts of oil additive employed are generally from 0.01to 2% based on the spray mixture. The oil additive can, for example, beadded to the spray tank in the desired concentration after the spraymixture has been prepared. Suitable oil additives include emulsifiableoil concentrates of mineral oils or, especially, of vegetable oils.Preferred vegetable oil concentrates comprise, for example, thefollowing 4 components (A) from 20 to 90% by weight of alkyl esters ofhigher fatty acids (C₄-C₂₂), (B) from 4 to 40% by weight of anionic ornon-ionic surfactants, (C) from 2 to 20% by weight of higher fatty acids(C₁₀-C₂₀), and (D) up to 140% by weight, based on the total amount ofcomponents (A) to (C), of hydrocarbons.

Especially preferred oil additives c) comprise alkyl esters of higherfatty acids (C₈-C₂₂), especially the C₁-C₄alkyl ester derivatives ofC₁₂-C₁₈ fatty acids, for example the methyl esters of lauric acid,palmitic acid and oleic acid. Those esters are known as methyl laurate(CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate(CAS-112-62-9). The application and action of the oil additives can beimproved by combining them with surface-active substances, for exampleanionic surfactants (B). Examples of suitable anionic surfactants arelisted in WO 97/34485 on pages 7 and 8. Preferred surface-activesubstances are anionic surfactants of the dodecylbenzylsulfonate type,especially the calcium salts thereof. The concentration of thesurface-active substances based on the total additive is generally from1 to 30% by weight.

Preferred higher fatty acids (C) have from 12 to 18 carbon atoms. Theaddition of an organic solvent (D) to the oil additive/surfactant/fattyacid mixture can, furthermore, bring about a further increase in action.Suitable solvents (D) are, for example, aromatic solvents, e.g.Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation) types. Theconcentration of those solvents can be from 10 to 80% by weight, of thetotal weight.

Such oil additives are described, for example, in U.S. Pat. No.4,834,908. They are especially preferred for the composition accordingto the invention. An especially preferred oil additive is known underthe name MERGE®.

The compositions according to the invention are suitable for all methodsof application that are customary in agriculture, for examplepre-emergence application, post-emergence application and seed dressing.In the case of seed dressing, from 0.001 to 10 g of safener/kg of seed,preferably from 0.05 to 2 g of safener/kg of seed, are generallyapplied. When the safener is applied in liquid form shortly beforesowing, with swelling of the seed, safener solutions are advantageouslyused that comprise the active ingredient in a concentration of from 1 to10 000 ppm, preferably from 100 to 1000 ppm.

For application, the safeners of formula II or combinations of thosesafeners with the herbicides of formula I and, optionally the oiladditives are advantageously processed, together with the adjuvantsconventionally employed in formulation technology, into formulations,for example into emulsifiable concentrates, coatable pastes, directlysprayable or dilutable solutions, dilute emulsions, wettable powders,soluble powders, dusts, granules or microcapsules. Such formulations aredescribed, for example, in WO 97/34485, on pages 9 to 13. Theformulations are prepared in known manner, for example by intimatelymixing and/or grinding the active ingredients with liquid or solidformulation adjuvants, for example solvents or solid carriers.Furthermore, surface-active compounds (surfactants) may also be used inpreparation of the formulations. Solvents and solid carriers that aresuitable for that purpose are mentioned, for example, in WO 97/34485 onpage 6.

Suitable surface-active compounds are, depending on the nature of theactive ingredient of formula I being formulated, non-ionic, cationicand/or anionic surfactants and mixtures of surfactants having goodemulsifying, dispersing and wetting properties. Examples of suitableanionic, non-ionic and cationic surfactants are listed, for example, inWO 97/34485 on pages 7 and 8.

Furthermore, the surfactants customarily employed in formulationtechnology, which are described, inter alia, in “Mc Cutcheon'sDetergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J.,1981, Stache, H., “Tensid-Taschenbuch”, Carl Hanser Verlag,Munich/Vienna, 1981 and M. and J. Ash, “Encyclopedia of Surfactants”,Vol I-III, Chemical Publishing Co., New York, 1980-81, are also suitablefor preparation of the herbicidal compositions according to theinvention.

The herbicidal formulations generally comprise from 0.1 to 99% byweight, especially from 0.1 to 95% by weight, of active ingredientmixture comprising a compound of formula I together with a compound offormula II, from 0.01 to 2% by weight of oil additive, from 1 to 99.9%by weight of a solid or liquid formulation adjuvant and from 0 to 25% byweight, especially from 0.1 to 25% by weight, of a surfactant. Whereascommercial products will preferably be formulated as concentrates, theend user will normally employ dilute formulations.

The compositions may also comprise further ingredients such asstabilisers, for example vegetable oils or epoxidised vegetables oils(epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, forexample silicone oil, preservatives, viscosity regulators, binders andtackifiers, as well as fertilisers or other active ingredients. Thereare various suitable methods and techniques for using the safeners offormula II or compositions comprising them for protecting cultivatedplants against the harmful effects of herbicides of formula I; thefollowing are examples:

i) Seed dressing

a) Dressing the seeds with a wettable powder formulation of a compoundof formula II by shaking in a vessel until the formulation is uniformlydistributed over the seed surface (dry dressing). Approximately from 1to 500 g of compound of formula II (from 4 g to 2 kg of wettable powder)are used per 100 kg of seed.

b) Dressing the seeds with an emulsifiable concentrate of a compound offormula II according to method a) (wet dressing).

c) Dressing by immersing the seed in a liquid formulation comprisingfrom 100 to 1000 ppm of a compound of formula II for from 1 to 72 hoursand, if desired, subsequently drying the seeds (immersion dressing).

Dressing the seed or treating the germinated seedlings are naturally thepreferred methods of application because the treatment with the activeingredient is directed wholly at the target crop. Generally from 1 to1000 g of antidote, preferably from 5 to 250 g of antidote, are used per100 kg of seed, although, depending on the method employed, which alsoallows the addition of other active ingredients or micronutrients,amounts that exceed or fall short of the specified concentration limitsmay be employed (repeat dressing).ii) Application in the form of a tank mixture

A liquid formulation of a mixture of antidote and herbicide (ratio ofthe one to the other from 10:1 to 1:100) is used, the rate ofapplication of herbicide being from 0.005 to 5.0 kg per hectare. Such atank mixture is applied before or after sowing.

iii) Application in the seed furrow

The compound of formula II is introduced into the open, sown seed furrowin the form of an emulsifiable concentrate, a wettable powder orgranules and, after the seed furrow has been covered, the herbicide isapplied pre-emergence in the normal manner.

iv) Controlled release of the active ingredient

The compound of formula II is applied in solution to granulated mineralcarriers or polymerised granules (urea-formaldehyde) and dried. Ifdesired, a coating may be applied (coated granules) which enables theactive ingredient to be released in metered amounts over a predeterminedperiod of time.

Preferred formulations have especially the following composition(%=percent by weight; ‘active ingredient mixture’ denotes the mixture ofthe compound of formula I with the compound of formula II)

Emulsifiable concentrates: active ingredient mixture: 1 to 90%,preferably 5 to 20% surface-active agent: 1 to 30%, preferably 10 to 20%liquid carrier: 5 to 94%, preferably 70 to 85% Dusts: active ingredientmixture: 0.1 to 10%, preferably 0.1 to 5% solid carrier: 99.9 to 90%,preferably 99.9 to 99% Suspension concentrates: active ingredientmixture: 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88to 30% surface-active agent: 1 to 40%, preferably 2 to 30% Wettablepowders: active ingredient mixture: 0.5 to 90%, preferably 1 to 80%surface-active agent: 0.5 to 20%, preferably 1 to 15% solid carrier: 5to 95%, preferably 15 to 90% Granules: active ingredient mixture: 0.1 to30%, preferably 0.1 to 15% solid carrier: 99.5 to 70%, preferably 97 to85%

The Examples that follow illustrate the invention further. They do notlimit the invention.

Formulation Examples for mixtures of herbicides of formula I andsafeners of formula II (%=percent by weight)

F1. Emulsifiable concentrates a) b) c) d) active ingredient mixture 5%10% 25% 50% calcium dodecylbenzenesulfonate 6% 8% 6% 8% castor oilpolyethylene glycol ether 4% — 4% 4% (36 mol of ethylene oxide)octylphenoxypolyethylene glycol ether — 4% — 2% (7-8 mol of ethyleneoxide) cyclohexanone — — 10% 20% aromatic C₉-C₁₂hydrocarbon mixture 85%78% 55% 16%

Emulsions of any desired concentration can be prepared from suchconcentrates by dilution with water.

F2. Solutions a) b) c) d) active ingredient mixture 5% 10% 50% 90%1-methoxy-3-(3-methoxy- — 20% 20% — propoxy)-propane polyethylene glycol(mol. wt. 400) 20% 10% — — N-methyl-2-pyrrolidone — — 30% 10% aromaticC₉-C₁₂hydrocarbon mixture 75% 60% — —

The solutions are suitable for application in the form of micro-drops.

F3. Wettable powders a) b) c) d) active ingredient mixture 5% 25% 50%80% sodium lignosulfonate 4% — 3% — sodium lauryl sulfate 2% 3% — 4%sodium disobutylnaphthalenesulfonate — 6% 5% 6% octylphenoxypolyethyleneglycol ether — 1% 2% — (7-8 mol of ethylene oxide) highly dispersedsilicic acid 1% 3% 5% 10% kaolin 88% 62% 35% —

The active ingredient is mixed with the adjuvants and the mixture isthoroughly ground in a suitable mill, affording wettable powders whichcan be diluted with water to give suspensions of any desiredconcentration.

F4. Coated granules a) b) c) active ingredient mixture 0.1% 5% 15%highly dispersed silicic acid 0.9% 2% 2% inorganic carrier material99.0% 93% 83% (

0.1-1 mm) for example CaCO₃ or SiO₂

The active ingredient is dissolved in methylene chloride, the solutionis sprayed onto the carrier, and the solvent is subsequently evaporatedoff in vacuo.

F5. Coated granules a) b) c) active ingredient mixture 0.1% 5% 15%polyethylene glycol (mol. wt. 200) 1.0% 2% 3% highly dispersed silicicacid 0.9% 1% 2% inorganic carrier material 98.0% 92% 80% (

0.1-1 mm) for example CaCO₃ or SiO₂

The finely ground active ingredient is uniformly applied, in a mixer, tothe carrier material moistened with polyethylene glycol, yieldingnon-dusty coated granules.

F6. Extruder granules a) b) c) d) active ingredient mixture 0.1% 3% 5%15% sodium lignosulfonate 1.5% 2% 3% 4% carboxymethylcellulose 1.4% 2%2% 2% kaolin 97.0% 93% 90% 79%

The active ingredient is mixed with the adjuvants, and the mixture isground, moistened with water, extruded and then dried in a stream ofair.

F7. Dusts a) b) c) active ingredient mixture 0.1% 1% 5% talcum 39.9% 49%35% kaolin 60.0% 50% 60%

Ready-to-use dusts are obtained by mixing the active ingredient with thecarriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) c) d) active ingredient mixture 3% 10%25% 50% ethylene glycol 5% 5% 5% 5% nonylphenoxypolyethylene glycol — 1%2% — ether (15 mol of ethylene oxide) sodium lignosulfonate 3% 3% 4% 5%carboxymethylcellulose 1% 1% 1% 1% 37% aqueous formaldehyde 0.2% 0.2%0.2% 0.2% solution silicone oil emulsion 0.8% 0.8% 0.8% 0.8% water 87%79% 62% 38%

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water.

It is often more practical to formulate the active ingredient of formulaI and the mixing partner of formula II separately and then, shortlybefore application, to bring them together in the applicator in thedesiring mixing ratio in the form of a “tank mixture” in water. Theability of the safeners of formula II to protect cultivated plants fromthe phytotoxic action of herbicides of formula I is illustrated in thefollowing Examples.

Biological Examples Examples B1, B2 and B3

Post-emergence applications of mixtures of a herbicide of formula I,wherein R₁ and R₃ are —C₂H₅; R₄ and R₅ together form a group Z_(z)—CR₁₄(R₁₅)—CR₁₆(R₁₇)—O—CR₁₈(R₁₉)—CR₂₀(R₂₁)— (Z₂), wherein R₁₄, R₁₅, R₁₆,R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ are hydrogen; and G is either hydrogen(=herbicide no. I₁) or (CH₃)₃CC(O)— (=herbicide no I₂), with a safenerof formula IIa, wherein R₂₂ is ethyl (=safener no. IIa₁), or of formulaIIb, wherein R₂₃ is ethyl (=safener no. IIb₁), to wheat and barley,together with 3 different weeds. The test plants are grown in pots undergreenhouse conditions until a post-application stage. A standard soil isused as the cultivation substrate. At a post-emergence stage, theherbicides, both alone and in admixture with safeners, are applied tothe test plants or to cultivated plants of which the seeds were dressedwith safeners. Application is carried out using an emulsion preparedfrom a 25% emulsifiable concentrate (Example F1, b)) of the testsubstances using 500 l of water/ha. The rates of application are matchedto the optimum dosages determined under field or greenhouse conditions.Evaluation of the tests is carried out after 9, 10, 20 and 24 days (100%action=complete destruction; 0% action=no phytotoxic action). Theresults obtained show that the safener used can significantly reduce thedamage caused to the cultivated plants by the herbicide of formula I.

Examples of the action of the composition according to the invention aregiven in Tables B1, B2 and B3.

TABLE B1 Post-emergence application of herbicide no I₁, alone and incombination with safener no. IIa₁, to summer wheat, hard wheat andLolium rigidum; evaluation 9 and 20 days after application. Herbicideno. I₁ [a.i. g/ha] 500 250 125 + Herbicide no. I₁ safener no. IIa₁Evaluation [a.i. g/ha] [a.i. g/ha] Plant [days] 250 125 60 125 60 30summer wheat 9 60 60 60 20 10 10 hard wheat 9 60 60 55 10 5 5 summerwheat 20 50 40 20 15 5 0 hard wheat 20 45 30 20 10 0 0 Lolium rigidum 20100 100 95 100 95 95

TABLE B2 Post-emergence application of herbicide no. I₁ atconcentrations of 125, 60, 30 and 15 g a.i./ha, alone and in combinationwith safener no. IIa₁ and IIb₁ at 30, 15, 8 and 4 g a.i./ha, to winterwheat and winter barley, and also Agrostis spica-venti, Alopecurusmyosuroides and Lolium rigidum; evaluation 10 days after application.Herbicide no. I₁ Herbicide no. I₁ [a.i. g/ha] [a.i. g/ha] 125 60 30 15125 60 30 15 + + Herbicide no. I₁ safener no. IIa₁ safener no. IIb₁[a.i. g/ha] [a.i. g/ha] [a.i. g/ha] Plant 125 60 30 15 30 15 8 4 30 15 84 winter 20 10 5 0 0 0 0 0 10 5 0 0 wheat winter 0 0 0 0 0 0 0 0 0 0 0 0barley Agrostis 80 80 70 70 80 80 70 60 80 80 70 70 sp. Alo- 90 80 80 5090 90 80 60 90 80 80 70 pecurus m. Lolium 80 60 60 60 80 80 70 60 80 8070 60 r.

TABLE B3 Post-emergence application of herbicide no. I₂ atconcentrations of 125, 60, 30 and 15 g a.i./ha, alone and in combinationwith safener no. IIa₁ and IIb₁ at 30, 15, 8 and 4 g a.i./ha, to winterwheat and winter barley, and also Agrostis spica-venti, Alopecurusmyosuroides and Lolium rigidum; evaluation 10 days and 24 days afterapplication. Herbicide no. I₂ Herbicide no. I₂ [a.i. g/ha] [a.i. g/ha]125 60 30 15 125 60 30 15 + + Herbicide no. I₂ safener no. IIa₁ safenerno. IIb₁ Evaluation [a.i. g/ha] [a.i. g/ha] [a.i. g/ha] Plant [days] 12560 30 15 30 15 8 4 30 15 8 4 winter wheat 10 30 20 10 0 0 0 0 0 20 10 00 winter barley 10 10 0 0 0 0 0 0 0 0 0 0 0 Agrostis sp. 10 90 80 70 6090 80 80 70 80 80 70 60 Alopecurus m. 10 90 80 80 60 90 80 70 40 90 8060 50 Lolium r. 10 80 80 70 70 80 80 70 70 80 80 70 70 winter wheat 24 00 0 0 0 0 0 0 0 0 0 0 winter barley 24 0 0 0 0 0 0 0 0 0 0 0 0

The same results are obtained where the active ingredient mixture isformulated according to the other Formulation Examples mentioned above.

1. A selectively herbicidal composition which, in addition to customaryinert formulation assistants, comprises as active ingredient a mixtureof a) a herbicidally effective amount of a compound of formula I

wherein R₁ and R₃ are, each independently of the other, ethyl,haloethyl, ethynyl, C₁- or C₂-alkoxy, C₁- or C₂-haloalkoxy, C₁- orC₂-alkylcarbonyl or C₁- or C₂-hydroxyalkyl; R₄ and R₅ together are agroup Z₂ which is CR₁₄(R₁₅)—CR₁₆(R₁₇)—O—CR₁₈(R₁₉)—CR₂₀(R₂₁)—; R₁₄, R₁₅,R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ are, each independently of the others,hydrogen, halogen, C₁-C₄alkyl or C₁-C₄haloalkyl, wherein an alkylenering may be fused or spiro-bound to the carbon atoms of the group Z₂,which alkylene ring, together with the carbon atoms of the group Z₂, towhich it is bonded, contains from 2 to 6 carbon atoms and may beinterrupted by oxygen, or the alkylene ring bridges at least one ringatom of the group Z₂; G is hydrogen, —C(X₁)—R₃₀, —C(X₂)—X₃—R₃₁,—C(X₄)—NR₃₂(R₃₃), —S(O)₂—R₃₄, —P(X₅)R₃₅R₃₆, —CH₂—X₆—R₃₇ or an alkalimetal, alkaline earth metal, sulfonium or ammonium cation; X₁, X₂, X₃,X₄, X₅ and X₆ are, each independently of the others, oxygen or sulfur;R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇ are, each independently of theothers, hydrogen, C₁-C₁₀alkyl, C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl,C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl, C₂-C₅-alkenyl, C₂-C₅haloalkenyl,C₃-C₈cycloalkyl, C₁-C₅alkylamino-C₁-C₅alkyl,di(C₁-C₅alkyl)amino-C₁-C₅alkyl, C₃-C₇cycloalkyl-C₁-C₅alkyl,C₁-C₅alkoxy-C₁-C₅alkyl, C₃-C₅alkenyloxy-C₁-C₅alkyl,C₃-C₅alkynyloxy-C₁-C₅alkyl, C₁-C₅alkylthio-C₁-C₅alkyl,C₁-C₅alkylsulfoxy-C₁-C₅alkyl, C₁-C₅-alkylsulfonyl-C₁-C₅alkyl,C₂-C₈alkylideneaminooxy-C₁-C₅alkyl, C₁-C₅alkylcarbonyl-C₁-C₅alkyl,C₁-C₅alkoxycarbonyl-C₁-C₅alkyl, C₁-C₅alkylaminocarbonyl-C₁-C₅alkyl,di(C₁-C₅alkyl)aminocarbonyl-C₁-C₅alkyl,C₁-C₅alkylcarbonylamino-C₁-C₅alkyl,C₁-C₅alkylcarbonyl-(C₁-C₅-alkyl)-amino-C₁-C₅alkyl, tri(C₁- orC₂-alkyl)silyl-C₁-C₅alkyl, phenyl, heteroaryl, phenyl-C₁-C₅alkyl,heteroaryl-C₁-C₅alkyl, phenoxy-C₁-C₅alkyl or heteroaryloxy-C₁-C₅alkyl,wherein the afore-mentioned aromatic rings may be substituted byhalogen, nitro, cyano, amino, di(C₁-C₄alkyl)amino, hydroxy, methoxy,ethoxy, methylthio, ethylthio, formyl, acetyl, propionyl, carboxyl,C₁-C₅alkoxycarbonyl or by C₁- or C₂-haloalkyl; R₃₄, R₃₅ and R₃₆ are, inaddition, C₁-C₁₀alkoxy, C₁-C₁₀haloalkoxy, C₁-C₅alkylamino,di(C₁-C₅-alkyl)amino, benzyloxy or phenoxy, wherein the aromatic ringsof the last two substituents may be substituted by halogen, nitro,cyano, amino, dimethylamino, hydroxy, methoxy, ethoxy, methylthio,ethylthio, formyl, acetyl, propionyl, carboxyl, C₁-C₅alkoxycarbonyl orby C₁- or C₂-haloalkyl; and R₃₇ is, in addition, C₁-C₁₀alkylcarbonyl, ora salt or diastereoisomer of a compound of formula I, and b) an amount,which is effective for antagonism of the herbicide, of a safener offormula IIa

wherein R₂₂ is hydrogen, or an alkali metal, alkaline earth metal,sulfonium or ammonium cation, or ethyl.
 2. A composition according toclaim 1, which comprises as active ingredient a mixture of a) aherbicidally effective amount of a herbicide of formula I, wherein R₁,R₃, R₄, R₅ and G are as defined in claim 1, and b) an amount, which iseffective for antagonism of the herbicide, of a safener of formula IIa,wherein R₂₂ is as defined in claim 1 for formula IIa.
 3. A compositionaccording to claim 1, wherein R₁ and R₃ in the compounds of formula Iare, each independently of the other, ethyl, haloethyl, ethynyl, C₁- orC₂-alkoxy or C₁- or C₂-haloalkoxy.
 4. A composition according to claim1, wherein R₄ and R₅ in the compounds of formula I together form a groupZ₂ which is —CR₁₄(R₁₅)—CR₁₆(R₁₇)—O—CR₁₈(R₁₉)—CR₂₀(R₂₁)—, wherein R₁₄,R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ are hydrogen.
 5. A compositionaccording to claim 1, wherein G in the compounds of formula I ishydrogen, —C(X₁)—R₃₀, —C(X₂)—X₃—R₃₁, —C(X₄)—NR₃₂(R₃₃), —S(O)₂—R₃₄,—P(X₅)R₃₅R₃₆, —CH₂—X₆—R₃₇ or an alkali metal, alkaline earth metal,sulfonium or ammonium cation; X₁, X₂, X₃, X₄, X₅ and X₆ are, eachindependently of the others, oxygen or sulfur; R₃₀, R₃₁, R₃₂, R₃₃, R₃₄,R₃₅, R₃₆ and R₃₇ are, each independently of the others, hydrogen,C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈cyanoalkyl, C₁-C₈nitroalkyl,C₁-C₈aminoalkyl, C₂-C₅-alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl,C₁-C₅alkylamino-C₁-C₂alkyl, di(C₁-C₅alkyl)amino-C₁-C₂alkyl,C₃-C₇cycloalkyl-C₁-C₂alkyl, C₁-C₄alkoxy-C₁-C₄alkyl,C₂-C₄alkenyloxy-C₁-C₄alkyl, C₃-C₄alkynyloxy-C₁-C₄alkyl,C₁-C₄alkylthio-C₁-C₄alkyl, C₁-C₄alkylsulfoxy-C₁-C₂alkyl,C₁-C₂-alkylsulfonyl-C₁-C₂alkyl, C₂-C₈alkylideneaminooxy-C₁-C₂-alkyl,C₁-C₅alkylcarbonyl-C₁-C₂alkyl, C₁-C₅alkoxycarbonyl-C₁-C₂alkyl,C₁-C₅alkylaminocarbonyl-C₁-C₂alkyl,di(C₁-C₄alkyl)aminocarbonyl-C₁-C₂alkyl,C₁-C₅alkylcarbonylamino-C₁-C₂alkyl,C₁-C₂alkylcarbonyl-(C₁-C₃alkyl)-amino-C₁-C₂alkyl, tri(C₁- orC₂-alkyl)silyl-C₁-C₃-alkyl, phenyl, heteroaryl, phenyl-C₁-C₂alkyl,heteroaryl-C₁-C₂alkyl, phenoxy-C₁-C₂alkyl or heteroaryloxy-C₁-C₂alkyl;R₃₄, R₃₅ and R₃₆ are, in addition, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₁-C₃alkylamino, di(C₁-C₃-alkyl)amino, benzyloxy or phenoxy, wherein thearomatic rings of the last two substituents may be substituted byhalogen, nitro, cyano, amino, dimethylamino, hydroxy, methoxy, ethoxy,methylthio, ethylthio, formyl, acetyl, propionyl, carboxyl,C₁-C₅alkoxycarbonyl or by C₁- or C₂-haloalkyl; and R₃₇ is, in addition,C₁-C₈alkylcarbonyl.
 6. A composition according to claim 5, wherein G ishydrogen, —C(X₁)—R₃₀, —C(X₂)—X₃—R₃₁, —C(X₄)—NR₃₂(R₃₃), —S(O)₂—R₃₄,—P(X₅)R₃₅R₃₆, —CH₂—X₆—R₃₇ or an alkali metal, alkaline earth metal,sulfonium or ammonium cation; X₁, X₂, X₃, X₄, X₅ and X₆ are, eachindependently of the others, oxygen or sulfur; R₃₀, R₃₁, R₃₂, R₃₃, R₃₄,R₃₅, R₃₆ and R₃₇ are, each independently of the others, hydrogen,C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₅alkenyl, C₂-C₅haloalkenyl,C₃-C₈-cycloalkyl, C₃-C₇cycloalkyl-C₁-C₂alkyl, C₁-C₄alkoxy-C₁-C₄alkyl,phenyl, heteroaryl, phenyl-C₁-C₂alkyl, heteroaryl-C₁-C₂alkyl,phenoxy-C₁-C₂alkyl or heteroaryloxy-C₁-C₂alkyl, R₃₄, R₃₅ and R₃₆ are, inaddition, C₁-C₆alkoxy, C₁-C₃alkylamino or di(C₁-C₃-alkyl)amino; and R₃₇is, in addition, C₁-C₈alkylcarbonyl.
 7. A method of selectivelycontrolling weeds and grasses in crops of useful plants, which comprisestreating the useful plants, their seeds or seedlings or the crop areathereof with, simultaneously or separately, a) a herbicidally effectiveamount of a herbicide of formula I as claimed in claim 1, b) an amount,which is effective for antagonism of the herbicide, of a safener offormula IIa and, optionally, c) an additive comprising an oil ofvegetable origin or an alkylated derivative thereof, or a mineral oil ora mixture thereof.
 8. A method according to claim 7, which comprisestreating crops of useful plants or crop areas for crops of useful plantswith from 0.001 to 2 kg/ha of a herbicide of formula I and an amount offrom 0.001 to 0.5 kg/ha of a safener of formula IIa.
 9. A methodaccording to claim 7, wherein the crops of useful plants are cereals,maize and sorghum.
 10. A composition according to claim 1, which alsocomprises, in addition to the formulation adjuvants, an oil additive inthe form of a vegetable oil concentrate consisting of the 4 components(A) from 20 to 90% by weight of an alkyl ester of a higher fatty acid(C₄-C₂₂), (B) from 4 to 40% by weight of an anionic surfactant, (C) from2 to 20% by weight of a higher fatty acid (C₁₀-C₂₀), and (D) up to 140%by weight, based on the total amount of components (A) to (C), of ahydrocarbon.
 11. A composition according to claim 10, wherein (A) is aC₁-C₄alkyl ester of a C₁₂-C₁₈ fatty acid, (B) is an anionic surfactantof the dodecylbenzylsulfonate type, (C) is a C₁₂-C₁₈ fatty acid, and (D)is an aromatic hydrocarbon.